WO1999001233A1 - Method for coating silicone elastomers - Google Patents
Method for coating silicone elastomers Download PDFInfo
- Publication number
- WO1999001233A1 WO1999001233A1 PCT/EP1998/003650 EP9803650W WO9901233A1 WO 1999001233 A1 WO1999001233 A1 WO 1999001233A1 EP 9803650 W EP9803650 W EP 9803650W WO 9901233 A1 WO9901233 A1 WO 9901233A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- coating
- silicone
- silicone elastomers
- coating agent
- silicone rubber
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
Definitions
- the invention relates to a method for coating silicone elastomers, in particular small areas ( ⁇ 100 mm 2 ) made of silicone elastomers.
- the method according to the invention above all enables coating in thicknesses ⁇ 300 ⁇ m.
- the coating compositions can be pigmented e.g. be electrically conductive with soot, e.g. to achieve electrically conductive contact points on silicone switch mats for telephone keyboards.
- the coating compositions can also be transparent or translucent, e.g. Coatings on printed keyboards (topcoat) to protect the printing against abrasion, hand sweat and other aggressive substances, e.g. Alcohol, detergents, cosmetics.
- silicone elastomers The coating of silicone elastomers is becoming increasingly important. Among other things, it is important the application of electrically conductive contact points on silicone elastomers for the production of switch mats.
- Fully automatic processes either involve punching out contact points from approximately 0.5 mm thick, electrically conductive, peroxidically cross-linked! Silicone rubber with subsequent fully automatic placement of the contact points in a heated mold, subsequent overmolding with non-conductive silicone rubber or the injection molding of the contact points with subsequent overmolding of non-conductive silicone rubber in an injection molding system with two injection units and a turntable mold.
- a switch mat made of silicone rubber is produced in the compression molding process without a conductive contact point and then printed on an electrically conductive silicone layer by means of screen or pad printing. In this case, only layer thicknesses between 1 and 10 ⁇ are achieved, which is not sufficient for a usual electrical contact resistance of ⁇ 100 ohms. For this reason, it is necessary to perform multiple printing operations with multiple burn-in operations.
- Silicon switching mats printed with symbols, numbers and characters must also be protected against abrasion with a top coat. This is done by spraying suitable clear lacquers based on silicone rubber or organic lacquer systems.
- the object of the invention was therefore to provide a simple method for coating silicone elastomers which does not have the disadvantages of the prior art. It has now been found that silicone elastomers can be coated by applying the coating agent in the form of drops or as a liquid jet with a metering pump and then curing it.
- the method according to the invention can be integrated into the fully automatic process for the production of switch mats, requires only low investment costs, it only requires a single hardening of the silicone rubber or the organic varnish, the process enables a high degree of flexibility when changing the design of the switch mat, the amounts of coating material are very high low, since there is no loss from overspray etc., the layer thicknesses are very reproducible and there is no disposal of overspray.
- the invention relates to the process for coating silicone elastomers, characterized in that the coating composition is in the form of drops or
- Liquid jet is applied to the silicone elastomer using a metering pump and then cured.
- One- or two-component paints on an organic basis can be used as coating agents.
- Liquid crosslinkable silicone rubber mixtures which contain a suitable vaporizable solvent and optionally carbon black can also be used.
- an organic lacquer preferably a polyurethane lacquer
- the surface of the silicone is preferably subjected to a corona treatment or gas flame treatment using known methods (cf. arcotec, Germany "HF corona treatment a brief summary” and "Pre-treatment with the gas flame") that a hydrophilic surface with a surface tension
- one-component paints are: Varnishes based on alkyd, acrylate, epoxy, polyvinyl acetate, polyester, polyvinyl chloride or polyurethane resins and
- a mixture of can be used as liquid crosslinkable silicone rubber mixtures
- d) optionally a solvent with a boiling point between 160 and 250 ° C.
- crosslinkable organopolysiloxane (a) is preferably a siloxane composed of units of the general formula (I)
- R 1 is a monovalent aliphatic radical having 1 to 8 carbon atoms and
- (a) is dimethylvinylsiloxy terminated.
- the organosiloxanes (a) according to the invention have viscosities of 0.01 to 200 Pas, very particularly preferably 0.2 to 200 Pas.
- the viscosities are determined according to DIN 53 019 at 20 ° C.
- branched polymers which can also be solid resins dissolved in solvents, they may still have up to a maximum of 10 mol% of all Si atoms, alkoxy or OH groups.
- Linear, cyclic or branched organopolysiloxanes composed of units of the general formula (II) can preferably be used as crosslinking agents (b) for the purposes of the invention.
- R 1 monovalent aliphatic radical with 1 to 8 carbon atoms
- the hydrogen siloxanes (b) used preferably have a viscosity of 0.01 to 5 Pas.
- a peroxide such as e.g. Aroyl or dialkyl peroxides used.
- a peroxide such as e.g. Aroyl or dialkyl peroxides used.
- examples include 2,4-dichlorobenzoyl peroxide, 4-methylbenzoyl peroxide, dicumyl peroxide and / or 2,5-bis-tert-butylperoxo-2,5-dimethylhexane.
- Pt (0) complexes with alkenylsiloxanes as ligands are preferably used as catalysts for the crosslinking reaction in catalytic amounts of 1 to 100 ppm Pt.
- Pt (0) complexes are e.g. Pt- (0) with the following ligands: 1,3-divinyl-tetramethyldisiloxane or 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane.
- Pt (0) complexes are e.g. Pt- (0) with the following ligands: 1,3-divinyl-tetramethyldisiloxane or 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane.
- examples of such preferred inhibitors are e.g. 1,3-divinyl-tetramethyldisiloxane, l, 3,5,7-tetravinyl-l
- Ethinylcyclohexanol in amounts of 50 to 10,000 ppm.
- the ratio of the SiH groups in component b) to the alkenyl groups in component a) is preferably 1.2: 1 to 10: 1.
- the carbon blacks (c) used are preferably finely divided carbon blacks with a BET surface area of 50 to 1200 m 2 / g.
- Compounds or mixtures which dissolve silicone polymers and have a boiling point or boiling range between 160 and 250 ° C. can be used as solvent (d).
- Linear or cyclic polydimethylsiloxanes or mixtures thereof are preferred. Decamethylcyclopentasiloxane is particularly preferred.
- the mixtures can also contain reinforcing fillers, such as e.g. contain finely divided silicas, which, if appropriate, are used in a hydrophobic manner by customary methods.
- reinforcing fillers such as e.g. contain finely divided silicas, which, if appropriate, are used in a hydrophobic manner by customary methods.
- micropumps that contain solvents can be used as metering pumps
- Mixing mixtures in small amounts can e.g. available from Eppendorf, Germany.
- the metering is preferably carried out via a distribution chamber in which a nozzle is also incorporated.
- the nozzle diameter is preferably between 0.1 to 1 mm.
- Continuously electronically controlled pumps, driven by a stepper motor, are also preferred
- Pump part consists of a sleeve and a non-circular shaft.
- the application is carried out in such a way that the nozzle end of the metering pump with the silicone elastomer is brought up to the substrate such that the distance between the nozzle end and the substrate is preferably up to 20 mm, preferably ⁇ 0.5 mm, and the Dosing is stopped by stopping the material flow and pulling the nozzles away.
- the viscosity of the overall mixture is preferably between 0.05 and 10 Pas.
- the curing can take place by means of hot air treatment or IR radiation.
- the hot air treatment is preferably carried out depending on the thickness of the coating
- a short-wave IR emitter with gold reflector with at least 1000 watts is preferably used for the IR radiation.
- a commercially available, electronically controlled, continuous metering pump was used, for quantities from 10 to 500 ⁇ l.
- the distributor had an inlet for the above-mentioned hose and, according to the number of coating surfaces desired (eg contact points), 11 mm long steel outlet pipes with an outer diameter of 0.8 mm and an inner diameter of 0.5 mm. These were made from commercially available syringe cannulas , by gluing them in the distributor plate with cyanoacrylate glue at the upper end and then using wire erosion at the lower end to clean them to the appropriate length.Precise drilling with 0.5 mm thick steel drills prevented pipe constriction due to run-in cyanoacrylate glue of 0.5 mm on the distributor plate and distributor chamber were sealed and screwed together with an O-ring made of fluororubber
- the distributor was clamped in a vertical lowering device, similar to a drill stand for hand drills, possibly with an electronically controlled lowering mechanism
- the substrate was positioned exactly in a substrate holder, the distributor was lowered to a distance of 0.5 mm from the outlet opening to the substrate. Only then was the coating compound metered. realizations (eg ring-shaped coatings or somewhat larger areas - eg 100 mm 2 in order to compensate for the capillary effects in these small coating areas).
- the distributor was raised again immediately after pumping.
- the still wet substrate was then fed to an IR radiator or a hot air treatment. This is where the coating composition is crosslinked and, if necessary, the solvent is evaporated.
- the switching mat thus obtained had a smooth surface and showed an average contact resistance of 13 ⁇ when pressed onto a circuit board with copper lines at a distance of 0.4 mm.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP98937492A EP0996509B1 (en) | 1997-06-30 | 1998-06-17 | Method for coating silicone elastomers |
JP50622299A JP2002511793A (en) | 1997-06-30 | 1998-06-17 | Method for coating silicone elastomers |
AT98937492T ATE235969T1 (en) | 1997-06-30 | 1998-06-17 | METHOD FOR COATING SILICONE ELASTOMERS |
DE59807751T DE59807751D1 (en) | 1997-06-30 | 1998-06-17 | METHOD FOR COATING SILICONE ELASTOMERS |
AU86269/98A AU8626998A (en) | 1997-06-30 | 1998-06-17 | Method for coating silicone elastomers |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19727525.7 | 1997-06-30 | ||
DE19727525A DE19727525A1 (en) | 1997-06-30 | 1997-06-30 | Process for coating silicone elastomers |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999001233A1 true WO1999001233A1 (en) | 1999-01-14 |
Family
ID=7833929
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1998/003650 WO1999001233A1 (en) | 1997-06-30 | 1998-06-17 | Method for coating silicone elastomers |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP0996509B1 (en) |
JP (1) | JP2002511793A (en) |
KR (1) | KR20010020556A (en) |
AT (1) | ATE235969T1 (en) |
AU (1) | AU8626998A (en) |
DE (2) | DE19727525A1 (en) |
HU (1) | HUP0003088A3 (en) |
ID (1) | ID24516A (en) |
TW (1) | TW445282B (en) |
WO (1) | WO1999001233A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4017839A1 (en) * | 1990-06-02 | 1991-12-05 | Zumtobel Ag | Tilt switch for standard lamps - has light in lamp disconnected from current circuit when lamp tilts or falls over |
KR100356860B1 (en) * | 2000-09-05 | 2002-10-18 | 현대자동차주식회사 | manufacturing method for door latch plate |
WO2006025953A1 (en) * | 2004-08-31 | 2006-03-09 | Dow Corning Corporation | Products having reduced permeability and methods for the preparation and use of the products |
US9421737B2 (en) | 2011-04-26 | 2016-08-23 | Aortech International Plc | Bonding process |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20010068107A (en) * | 2001-04-24 | 2001-07-13 | 안현화 | Key pad coating method and apparatus |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1014687A (en) * | 1963-06-20 | 1965-12-31 | Ici Ltd | Method of coating with organopolysiloxane elastomers |
US3460975A (en) * | 1965-03-19 | 1969-08-12 | Dow Corning | Tack-free silicone rubber articles for medical use |
GB2045824A (en) * | 1979-03-16 | 1980-11-05 | Dow Corning Ltd | Treatment of cured silicone elastomer |
GB2107923A (en) * | 1979-09-25 | 1983-05-05 | Dukhovskoi Evgeny A | Apparatus for modifying the surface of rubber articles |
CH653109A5 (en) * | 1982-03-09 | 1985-12-13 | Bbc Brown Boveri & Cie | Process for producing a chemically resistant composite material suitable for elastic gaskets |
US5024863A (en) * | 1990-02-02 | 1991-06-18 | Jmk International, Inc. | Engine gasket with oil impermeable surface |
EP0575798A1 (en) * | 1992-06-19 | 1993-12-29 | Fuji Polymertech Co., Ltd | Process for producing finger-touch key for manipulation switch |
US5338574A (en) * | 1993-03-30 | 1994-08-16 | Dow Corning Corporation | Method for producing a painted silicone elastomer |
WO1995020006A1 (en) * | 1994-01-21 | 1995-07-27 | Commonwealth Scientific And Industrial Research Organisation | Surface treatment of polymers |
US5677007A (en) * | 1996-08-13 | 1997-10-14 | Silitek Corporation | Method for coating silicone rubber keyboards |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3144084C2 (en) * | 1981-11-06 | 1988-08-18 | Preh, Elektrofeinmechanische Werke Jakob Preh Nachf. Gmbh & Co, 8740 Bad Neustadt | Process for the manufacture of a contact mat suitable for a push button panel |
-
1997
- 1997-06-30 DE DE19727525A patent/DE19727525A1/en not_active Ceased
-
1998
- 1998-06-15 TW TW087109426A patent/TW445282B/en not_active IP Right Cessation
- 1998-06-17 AT AT98937492T patent/ATE235969T1/en not_active IP Right Cessation
- 1998-06-17 EP EP98937492A patent/EP0996509B1/en not_active Expired - Lifetime
- 1998-06-17 DE DE59807751T patent/DE59807751D1/en not_active Expired - Fee Related
- 1998-06-17 ID IDW991708A patent/ID24516A/en unknown
- 1998-06-17 HU HU0003088A patent/HUP0003088A3/en unknown
- 1998-06-17 KR KR1019997012425A patent/KR20010020556A/en not_active Application Discontinuation
- 1998-06-17 WO PCT/EP1998/003650 patent/WO1999001233A1/en not_active Application Discontinuation
- 1998-06-17 JP JP50622299A patent/JP2002511793A/en active Pending
- 1998-06-17 AU AU86269/98A patent/AU8626998A/en not_active Abandoned
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1014687A (en) * | 1963-06-20 | 1965-12-31 | Ici Ltd | Method of coating with organopolysiloxane elastomers |
US3460975A (en) * | 1965-03-19 | 1969-08-12 | Dow Corning | Tack-free silicone rubber articles for medical use |
GB2045824A (en) * | 1979-03-16 | 1980-11-05 | Dow Corning Ltd | Treatment of cured silicone elastomer |
GB2107923A (en) * | 1979-09-25 | 1983-05-05 | Dukhovskoi Evgeny A | Apparatus for modifying the surface of rubber articles |
CH653109A5 (en) * | 1982-03-09 | 1985-12-13 | Bbc Brown Boveri & Cie | Process for producing a chemically resistant composite material suitable for elastic gaskets |
US5024863A (en) * | 1990-02-02 | 1991-06-18 | Jmk International, Inc. | Engine gasket with oil impermeable surface |
EP0575798A1 (en) * | 1992-06-19 | 1993-12-29 | Fuji Polymertech Co., Ltd | Process for producing finger-touch key for manipulation switch |
US5338574A (en) * | 1993-03-30 | 1994-08-16 | Dow Corning Corporation | Method for producing a painted silicone elastomer |
WO1995020006A1 (en) * | 1994-01-21 | 1995-07-27 | Commonwealth Scientific And Industrial Research Organisation | Surface treatment of polymers |
US5677007A (en) * | 1996-08-13 | 1997-10-14 | Silitek Corporation | Method for coating silicone rubber keyboards |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4017839A1 (en) * | 1990-06-02 | 1991-12-05 | Zumtobel Ag | Tilt switch for standard lamps - has light in lamp disconnected from current circuit when lamp tilts or falls over |
KR100356860B1 (en) * | 2000-09-05 | 2002-10-18 | 현대자동차주식회사 | manufacturing method for door latch plate |
WO2006025953A1 (en) * | 2004-08-31 | 2006-03-09 | Dow Corning Corporation | Products having reduced permeability and methods for the preparation and use of the products |
US9421737B2 (en) | 2011-04-26 | 2016-08-23 | Aortech International Plc | Bonding process |
US9809016B2 (en) | 2011-04-26 | 2017-11-07 | Aortech International Plc | Bonding process |
US10195834B2 (en) | 2011-04-26 | 2019-02-05 | Aortech International Plc | Bonding process |
Also Published As
Publication number | Publication date |
---|---|
TW445282B (en) | 2001-07-11 |
EP0996509A1 (en) | 2000-05-03 |
KR20010020556A (en) | 2001-03-15 |
HUP0003088A3 (en) | 2003-02-28 |
DE59807751D1 (en) | 2003-05-08 |
AU8626998A (en) | 1999-01-25 |
ID24516A (en) | 2000-07-20 |
JP2002511793A (en) | 2002-04-16 |
HUP0003088A2 (en) | 2000-12-28 |
DE19727525A1 (en) | 1999-01-07 |
EP0996509B1 (en) | 2003-04-02 |
ATE235969T1 (en) | 2003-04-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE2644555C2 (en) | ||
DE3012772C2 (en) | Silicone composition | |
DE3049726C2 (en) | Electrically conductive part and process for its manufacture | |
DE3120534C2 (en) | ||
DE3008220C2 (en) | Process for the production of moldings using a silicone mold release agent | |
CN107428073A (en) | For preparing the silicon composition of elastomer formation part by ballistic processes | |
DE69911530T2 (en) | Curable silicone composition | |
DE2415554A1 (en) | HIGH STRENGTH ORGANOPOLYSILOXANE COMPOSITIONS | |
DE2422846B2 (en) | PROCESS FOR THE PRODUCTION OF ORGANOPOLYSILOXANE COMPOUNDS | |
CN107428074A (en) | For the crosslinkable silicon composition for the formed body that highly transparent is prepared by ballistic processes | |
US20200216692A1 (en) | Silicone 3D Printing Ink | |
EP0996509B1 (en) | Method for coating silicone elastomers | |
EP1238013B1 (en) | Addition cross-linked silicon rubber mixtures | |
DE2902436A1 (en) | PROCESS FOR PRODUCING SOLVENT-FREE SILICONE RESINS AND PRODUCTS THEREOF | |
EP3341441A1 (en) | Siloxane resin compositions | |
EP0993488B1 (en) | Cross-linkable liquid silicon rubber mixtures, method for the production thereof, method for producing electrically conductive contact points and the use thereof | |
DE3918328A1 (en) | HEAT-CURABLE COMPOSITIONS | |
DE1546410C3 (en) | Process for improving the abrasion resistance of siloxane impregnated papers and paper products | |
DE1291122B (en) | Manufacture of embedding compounds that harden with platinum catalysts | |
WO2003095547A2 (en) | Functionalised polyhedral oligomer silicon-oxygen clusters as cross-linking agents | |
DE19946916A1 (en) | Mold release agent for thermoset molded parts | |
DE3115563A1 (en) | METHOD FOR PRODUCING STICKY MATERIALS TO COVER REPELLENT | |
EP1213308A1 (en) | Releasable film for surface protection | |
DE102005023378B3 (en) | Solvent-free coating material, useful for in-mould-coating, comprises component from an aliphatic isocyanate and component with a cross-linkable binder | |
CZ9904782A3 (en) | Coating process of silicon elastomers |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE GH GM GW HU ID IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW SD SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 1019997012425 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: PV1999-4782 Country of ref document: CZ |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1998937492 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 09446938 Country of ref document: US |
|
WWP | Wipo information: published in national office |
Ref document number: 1998937492 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
NENP | Non-entry into the national phase |
Ref country code: CA |
|
WWP | Wipo information: published in national office |
Ref document number: PV1999-4782 Country of ref document: CZ |
|
WWP | Wipo information: published in national office |
Ref document number: 1019997012425 Country of ref document: KR |
|
WWR | Wipo information: refused in national office |
Ref document number: PV1999-4782 Country of ref document: CZ |
|
WWG | Wipo information: grant in national office |
Ref document number: 1998937492 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1019997012425 Country of ref document: KR |